KR100252225B1 - Base resin for photoresist using ultra-violet ray for fabrication of semiconductor device, its manufacturing method and photoresist using ultra-violet ray comprosing the base resin - Google Patents

Base resin for photoresist using ultra-violet ray for fabrication of semiconductor device, its manufacturing method and photoresist using ultra-violet ray comprosing the base resin Download PDF

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KR100252225B1
KR100252225B1 KR1019990042848A KR19990042848A KR100252225B1 KR 100252225 B1 KR100252225 B1 KR 100252225B1 KR 1019990042848 A KR1019990042848 A KR 1019990042848A KR 19990042848 A KR19990042848 A KR 19990042848A KR 100252225 B1 KR100252225 B1 KR 100252225B1
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resin
photoresist
photoresist composition
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이성호
신소영
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윤종용
삼성전자주식회사
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Materials For Photolithography (AREA)

Abstract

PURPOSE: A structural resin for deep UV exposing photoresist composition and its preparation method are provided to use the resin to accomplish the exposure process by using deep UV as light source in the photolithographic process in the semiconductor production. CONSTITUTION: The structural resin comprises t-butoxycarbonyl oxystyrene (TBS) chain extended resin represented by the following formula 1 (R1 and R2 are hydrogen or alkyl group having C1-C5 including methyl or ethyl group; R5 is isopropyl group; m is natural number of 100-1,000,000 and n is natural number of 1-100). The resin is prepared by polymerizing TBS with inifer containing disulfide to synthesize TBS oligomer having TBS repeating units by deep UV as a light source in the lithographic process. The resin is prepared by extending chains of TBS oligomer to 4-thiol-alpha,alpha'-alkylbenzyl-4-thiolphenyl ester as a connector molecules.

Description

반도체장치의 제조를 위한 원자외선 노광용 포토레지스트 조성용 구조제 수지와 그 제조방법 및 그 구조제 수지를 포함하는 원자외선 노광용 포토레지스트 조성물{Base resin for photoresist using ultra-violet ray for fabrication of semiconductor device, its manufacturing method and photoresist using ultra-violet ray comprosing the base resin}Structural resin for composition of photoresist for exposure to ultraviolet rays for the manufacture of semiconductor devices, and manufacturing method thereof and photoresist composition for exposure to ultraviolet rays comprising the structural resin manufacturing method and photoresist using ultra-violet ray comprosing the base resin}

본 발명은 반도체장치의 제조를 위한 원자외선 노광용 포토레지스트 조성용 구조제 수지와 그 제조방법 및 그 구조제 수지를 포함하는 원자외선 노광용 포토레지스트 조성물에 관한 것으로서, 보다 상세하게는 193nm의 파장대의 광에 대하여 투명한 구조를 갖는 반도체장치의 제조를 위한 원자외선 노광용 포토레지스트 조성용 구조제 수지와 그 제조방법 및 그 구조제 수지를 포함하는 원자외선 노광용 포토레지스트 조성물에 관한 것이다.The present invention relates to a photoresist composition for far ultraviolet exposure photoresist composition for manufacturing a semiconductor device, a method of manufacturing the same, and a photoresist composition for far ultraviolet exposure including the structural resin, and more particularly, to light in a wavelength range of 193 nm. The present invention relates to a far-infrared exposure photoresist composition structural resin for producing a semiconductor device having a transparent structure, a manufacturing method thereof, and a far-resistance photoresist composition containing the structural resin.

반도체 장치의 제조공정 중에서 사진식각공정(Photolithography)이라 함은 웨이퍼에 포토레지스트를 도포하고, 사전에 설계된 바 대로의 패턴을 전사하고, 전사된 패턴에 따라 적절하게 깎아내는 식각공정을 통하여 전자회로를 구성하는 작업으로 매우 중요한 작업의 하나이다.Photolithography is a process of manufacturing semiconductor devices by applying a photoresist to a wafer, transferring a pattern as previously designed, and etching the electronic circuit appropriately according to the transferred pattern. It is one of the very important tasks to configure.

상기한 사진식각공정에서 사용되는 포토레지스트(Photoresist)는 후속의 식각공정에서 식각되어야 하는 부분과 식각되지 않아야 하는 부분을 구별하는 역할을 하는 것으로서, 감광성 고분자가 사용되며, 감광성 고분자는 자외선(Ultra-violet)이나 전자빔(Electron-beam) 또는 엑스선(X-ray)과 같은 광의 작용에 의하여 단시간내에 화학적, 물리적 변화를 일으켜 용제(Developer)에 대한 용해도의 변화를 나타내는 물질이나 조성물이 될 수 있다.The photoresist used in the photolithography process serves to distinguish between the portion that should be etched and the portion that should not be etched in a subsequent etching process, and a photosensitive polymer is used, and the photosensitive polymer is ultraviolet (Ultra-). By the action of light such as violet, electron-beam or X-ray, it may be a material or composition that exhibits a change in solubility in a solvent by causing chemical and physical changes in a short time.

특히, 반도체장치 제조에서 사용되는 포토레지스트는 미크론(micron) 이하의 미세형상을 구현할 수 있는 것이어야 하며, 역시 빛에너지에 의하여 분해 또는 가교반응이 일어나 그 용해특성이 변화하는 물질로서, 포토리소그래피공정에서는 반도체장치를 제조하는 데 사용되는 웨이퍼의 표면에 상기한 바와 같은 감광특성을 갖는 포토레지스트를 균일하게 도포하고, 그 위에 소정의 패턴이 형성되어 있는 마스크(Mask)를 위치시킨 후, 상기 마스크 상으로 일정수준 이상의 에너지를 갖는 빛을 조사함으로써 상기 마스크에 의한 빛의 선택적 투과로 인한 상기 웨이퍼 상의 포토레지스트를 패턴에 따라 감광시키도록 한다. 빛의 조사에 의한 감광후에는 상기 포토레지스트는 빛의 조사에 의하여 화학적 또는 물리적 변화에 따라 빛이 조사된 영역과 빛이 조사되지 않은 영역 사이에서 용해도차를 나타내게 되며, 적절한 용매의 사용에 의하여 높은 용해도를 갖는 포토레지스트부분만 제거되고, 낮은 용해도를 갖는 포토레지스트부분은 제거되지 않고 잔류되도록 함으로써 잔류하는 포토레지스트에 의하여 그 하방의 웨이퍼가 식각공정 동안에 식각되지 않고 보호될 수 있으며, 그에 따라 마스크에 나타난 패턴이 그대로 웨이퍼 상으로 전사될 수 있게 된다.In particular, the photoresist used in the manufacture of semiconductor devices should be capable of realizing a micron or less micron, and is also a material whose decomposition characteristics are changed due to decomposition or crosslinking reaction caused by light energy. In the present invention, a photoresist having the above photosensitivity is uniformly applied to the surface of a wafer used for manufacturing a semiconductor device, and a mask having a predetermined pattern formed thereon is placed thereon. By irradiating light having a predetermined level or more energy to the photoresist on the wafer due to the selective transmission of the light by the mask according to the pattern. After photosensitization by irradiation of light, the photoresist exhibits a difference in solubility between the areas irradiated with light and the areas not irradiated with light due to chemical or physical changes due to light irradiation. Only the photoresist portion having solubility is removed, and the photoresist portion having low solubility is left unremoved so that the underlying wafer can be protected without being etched during the etching process by the remaining photoresist, thereby The pattern shown can be transferred onto the wafer as it is.

포토레지스트는 음성 포토레지스트(Negative Photoresist)와 양성 포토레지스트(Positive Photoresist)로 대별될 수 있다.Photoresists can be roughly classified into negative photoresist and positive photoresist.

음성 포토레지스트는 노광에 의해 가교(Cross-linking), 광이량화(Photo-dimerization) 등의 반응으로 분자량이 크게 증가하면서 용해성을 저하시켜 용해도차를 나타내며, 열적특성 및 내화학성 등이 현저하게 개선되어 양성 포토레지스트에 비하여 먼저 상용화되었다. 상용화된 음성 포토레지스트로는 폴리비닐신나메이트(Polyvinylcinnamate), 고리화된 고무(Cyclized Rubber), 비스아릴아지드(Bisarylazide), 폴리비닐알코올(PVA ; Polyvinylalcohol), 카제인(Casein), 젤라틴(Gelatine) 및 암모늄디크로메이트(Ammoniumdichromate) 등을 예로 들 수 있다. 그러나, 이러한 종래의 음성 포토레지스트들은 일반적으로 현상(development)시에 패턴의 팽윤(swelling) 현상이 일어나 해상력이 2 내지 3㎛ 정도에 불과하여 단지 강한 부식액을 사용하는 공정이나, 집적도가 낮은 반도체장치의 제조용으로 사용되며, 고집적도 반도체장치 제조공장에서는 이용되지 못한다는 단점이 있다.Negative photoresist shows solubility difference by decreasing solubility while increasing molecular weight by reaction such as cross-linking and photodimerization by exposure, and remarkably improving thermal characteristics and chemical resistance. It was first commercialized compared to the positive photoresist. Commercially available negative photoresists include polyvinylcinnamate, cyclized rubber, bisarylazide, polyvinyl alcohol (PVA; Polyvinylalcohol), casein, gelatin (Gelatine) And ammonium dichromate. However, these conventional negative photoresists generally have a pattern swelling during development, and have a resolution of only 2 to 3 µm, so that only a strong corrosion solution is used, but a low integration semiconductor device. It is used for manufacturing, and has a disadvantage that it cannot be used in a highly integrated semiconductor device manufacturing plant.

한편, 양성 포토레지스트는 노광에 의해 분해, 분자쇄절단(Chain Scission)등이 일어나 용해성 증가시켜 용해도차를 나타내며, 상기한 음성 포토레지스트와는 반대적인 특성들을 나타낸다. 상용화된 양성 포토레지스트로는 근자외선(Near Ultraviolet) 영역용의 디아조나프토퀴논(Diazonaphthoquinone)과 노볼락수지(Novolac Resin)가 혼합된 노볼락수지계와 원자외선(Deep Ultraviolet), 전자빔 또는 엑스선 용의 폴리메틸메타크릴레이트(PMMA ; Polymethylmethacrylate)계를 예로 들 수 있다. 양성 포토레지스트는 음성 포토레지스트와는 달리 팽윤현상이 적으며, 내에칭성이 뛰어나고, 특히 해상력이 높아 고집적도 반도체장치 제조공정에서 주로 사용되고 있다.On the other hand, the positive photoresist is decomposed by exposure, the molecular scission (Chain Scission) and the like to increase the solubility shows a difference in solubility, and exhibits the characteristics opposite to the negative photoresist described above. Commercially available positive photoresists include novolac resins, deep ultraviolets, electron beams or X-rays in which diazonaphthoquinone and Novolac Resin are mixed for the near ultraviolet region. Polymethyl methacrylate (PMMA; Polymethylmethacrylate) type is mentioned. Positive photoresist, unlike negative photoresist, has less swelling, excellent etch resistance, and particularly high resolution and is mainly used in high-density semiconductor device manufacturing processes.

특히, 광원으로서의 근자외선 영역의 광은 초고압 수은등을 사용하며, 436nm의 지-선(G-line), 405nm의 에이취-선(H-line) 및 365nm의 아이-선(I-line) 등 특별히 강한 세기(intensity)를 갖는 광선들을 얻을 수 있기 때문에 포토레지스트의 감도가 약간 낮은 경우에도 사용이 가능한 경우가 많으며, 지-선에 감광하는 포토레지스트는 0.45 내지 0.5㎛의 해상도를 나타내어 4M DRAM의 반도체장치의 제조를 위한 패턴의 구현이 가능하며, 아이-선에 감광하는 포토레지스트는 16M DRAM 정도까지의 반도체장치의 제조를 위한 서브미크론(submicron) 패턴의 구현이 가능한 것으로 알려져 있다.In particular, the light in the near-ultraviolet region as a light source uses an ultra-high pressure mercury lamp, and specifically, a G-line of 436 nm, an H-line of 405 nm, and an I-line of 365 nm. Since light rays with strong intensity can be obtained, the photoresist is often used even when the sensitivity of the photoresist is slightly low. It is known that a pattern for manufacturing a device can be implemented, and a photoresist photosensitive to eye lines can realize a submicron pattern for manufacturing a semiconductor device up to about 16M DRAM.

한편, 파장이 길수록 포토레지스트막과 산화막 등을 포함하는 전체 막질간에서의 회절 및 간섭 등의 영향으로 미세선폭의 구현을 어렵게 하고 있기 때문에, 고집적화된 반도체장치의 제조를 위하여는 패턴의 해상도를 높일 수 있어야 하며, 이를 위하여는 근자외선이나 중자외선(Mid-ultraviolet)에 비하여 보다 짧은 파장을 갖는 원자외선 영역의 광 또는 그보다 단파장의 광의 사용이 바람직하기는 하다.On the other hand, the longer the wavelength, the more difficult it is to implement the fine line width under the influence of diffraction and interference between the entire film including the photoresist film, the oxide film and the like, so that the resolution of the pattern is increased to manufacture a highly integrated semiconductor device. For this purpose, it is preferable to use light in the far ultraviolet region having shorter wavelength or shorter wavelength than the near ultraviolet or mid-ultraviolet.

최근 원자외선 노광용 스테퍼가 고집적 반도체장치의 제조에 적용되기 시작함에 따라 원자외선 노광용 포토레지스트의 개발이 적극 요구되고 있으며, 해상도 및 초점심도(DOF ; Depth of Focus)의 마진(Margin) 확보를 위한 원자외선 노광용 포토레지스트들이 개발되고 있으며, 상용화된 것의 예로는 티-부틸옥시카르보닐옥시기(t-BOC ; tert-buthyloxy-carbonyloxy group)를 보호기로 하는 폴리-파라-(티-부틸옥시카르보닐옥시)스티렌(Poly-p-(t-butyloxy-carbonyloxy)styrene)과 광산 발생제(Photoacid Generator)인 오늄염(Onium Salt)의 조합으로 된 포토레지스트, 역시 티-부틸옥시카르보닐옥시기를 보호기로 하는 폴리비닐히드록시페놀(PVHP ; Poly Vinyl Hydroxy Phenol)을 비롯하여 248nm에서 강한 세기를 갖는 광선을 내는 불화크립톤 엑시머 레이저(Krypton Fluoride Eximer Laser)노광용 포토레지스트 및 개량된 노볼락수지에 벤조페논계 감광제(PAC ; Photo Active Cmpounds)를 혼합한 조성물을 들 수 있다.Recently, as the stepper for ultraviolet exposure has been applied to the manufacture of highly integrated semiconductor devices, the development of photoresist for far ultraviolet exposure is actively required, and the circle for securing the margin of resolution and depth of focus (DOF) is required. Photoresists for ultraviolet exposure have been developed, and examples of commercialized ones include poly-para- (thi-butyloxycarbonyloxy having a tert-buthyloxy-carbonyloxy group (t-BOC) as a protecting group. Photoresist made of a combination of styrene (poly-p- (t-butyloxy-carbonyloxy) styrene) and photoacid generator (Onium Salt), which also contains a thi-butyloxycarbonyloxy group as a protecting group. Polyvinyl hydroxyphenol (PVHP), including krypton fluoride excimer laser with strong intensity at 248 nm Krypton Fluoride Eximer Laser) A composition in which a benzophenone-based photosensitive agent (PAC; Photo Active Cmpounds) is mixed with a photoresist for exposure and an improved novolak resin.

그러나, 상기한 바와 같은 종래의 포토레지스트들은 최근 개발되어 상용화된 광원인 불화아르곤 엑시머 레이저(Argon Fluoride Eximer Laser)와 같은 193nm 파장대의 광에 적용시키는 경우 광흡수를 일으켜 생산성 및 해상도의 측면에서 반도체장치의 양산에 적절치 못한 것으로 나타났다.However, the conventional photoresist as described above is a semiconductor device in terms of productivity and resolution in the light absorption when applied to the light of 193nm wavelength, such as Argon Fluoride Eximer Laser (Argon Fluoride Eximer Laser) which is a recently developed and commercial light source It was found to be inappropriate for mass production.

또한, 248nm에서 광흡수를 최소화할 수 있는 포토레지스트재료로서 아크릴계 수지를 사용하는 포토레지스트가 개발되긴 하였으나, 에칭에 취약성을 나타내기 때문에 현상 후, 별도의 후처리공정을 하거나 또는 포토레지스트를 구성하는 수지를 변형하여야만 하는 문제점이 있었다.In addition, a photoresist using an acrylic resin has been developed as a photoresist material capable of minimizing light absorption at 248 nm. However, since it exhibits fragility in etching, a separate post-treatment process or development of a photoresist is performed after development. There was a problem that the resin must be modified.

따라서, 193nm 정도의 단파장을 발생시키는 불화아르곤 엑시머 레이저에 적용시킬 수 있는 원자외선 노광용 포토레지스트의 개발 필요성은 여전히 존재하고 있는 것이다.Therefore, there is still a need to develop a photoresist for far ultraviolet exposure that can be applied to an argon fluoride excimer laser generating a short wavelength of about 193 nm.

본 발명의 목적은, 반도체장치의 제조를 위한 공정 중 포토리소그래피공정에서 광원으로서 원자외선을 사용하여 노광할 수 있는 원자외선 노광용 포토레지스트 조성용 구조제 수지를 제공하는 데 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a structural resin for photoresist composition for ultra-violet exposure, which can be exposed using ultraviolet rays as a light source in a photolithography step in the process of manufacturing a semiconductor device.

본 발명의 다른 목적은 원자외선을 사용하여 노광할 수 있는 원자외선 노광용 포토레지스트 조성용 구조제 수지를 제조하는 제조방법을 제공하는 데 있다.Another object of the present invention is to provide a manufacturing method for producing a structural resin for composition for photoresist for far ultraviolet exposure that can be exposed using far ultraviolet rays.

본 발명의 또다른 목적은 원자외선을 사용하여 노광할 수 있는 원자외선 노광용 포토레지스트 조성용 구조제 수지를 포함하는 원자외선 노광용 포토레지스트 조성물을 제공하는 데 있다.Still another object of the present invention is to provide a photoresist composition for exposure to far ultraviolet rays, including a structural resin for photoresist composition for exposure to far ultraviolet rays that can be exposed using far ultraviolet rays.

상기 목적을 달성하기 위한 본 발명에 따른 반도체장치의 제조를 위한 공정 중 포토리소그래피공정에서 광원으로서 원자외선을 사용하여 노광할 수 있는 원자외선 노광용 포토레지스트 조성용 구조제 수지는, 하기 화학식1과 같은 티비에스쇄연장수지로 구성된다.Structural resin for photoresist composition for far ultraviolet light exposure that can be exposed using far ultraviolet light as a light source in a photolithography process in the process for manufacturing a semiconductor device according to the present invention for achieving the above object, as shown in Formula 1 It is composed of S chain extension resin.

상기에서 R1및 R2는 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 5의 알킬기이고, R5는 이소프로필기이며, m은 100 내지 1,000,000의 자연수이고, n은 1 내지 100의 자연수임.In the above, R 1 and R 2 are hydrogen or a methyl group, alkyl group having 1 to 5 carbon atoms such as ethyl group, R 5 is isopropyl group, m is a natural number of 100 to 1,000,000, n is a natural number of 1 to 100.

상기 화학식1과 같은 티비에스쇄연장수지의 제조방법은 하기 화학식2에 나타난 바와 같이 티-부톡시카르보닐옥시스티렌을 디술피드를 포함하는 이니퍼(Inifer)를 사용하여 중합시켜 티비에스를 반복단위로 하는 티비에스올리고머를 합성하고, 하기 화학식3과 같이 상기 티비에스올리고머를 커넥터로서 4-티올-α,α'-알킬벤질-4-티올페닐에스터로 쇄연장시켜 수득된다.In the manufacturing method of the TBS chain extension resin as in Chemical Formula 1, as shown in the following Chemical Formula 2, thi-butoxycarbonyloxystyrene is polymerized using an inifer containing disulfide (Inifer) to repeat the TBS. It is obtained by synthesizing a TBS oligomer and chain-extending the TBS oligomer with 4-thiol-α, α'-alkylbenzyl-4-thiolphenyl ester as a connector as shown in the following formula (3).

상기에서 R5는 이소프로필기이며, R6및 R7은 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 3의 알킬기이고, m은 100 내지 1,000,000의 자연수임.In the above, R 5 is an isopropyl group, R 6 and R 7 is hydrogen or an alkyl group having 1 to 3 carbon atoms such as methyl group, ethyl group, m is a natural number of 100 to 1,000,000.

상기에서 R1및 R2는 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 5의 알킬기이고, R5는 이소프로필기이며, R6및 R7은 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 3의 알킬기이고, m은 100 내지 1,000,000의 자연수이고, n은 1 내지 100의 자연수임.In the above, R 1 and R 2 are hydrogen or methyl group, alkyl group of 1 to 5 carbon atoms such as ethyl group, R 5 is isopropyl group, R 6 and R 7 is hydrogen or methyl group, alkyl group of 1 to 3 carbon atoms such as ethyl group And m is a natural number of 100 to 1,000,000, and n is a natural number of 1 to 100.

또한, 본 발명에 따른 원자외선 노광용 포토레지스트 조성물은, 구조제 수지로서 상기 화학식1의 티비에스쇄연장수지 10 내지 20 중량%, 감광제 5 내지 10 중량%, 첨가제 0.1 내지 2 중량% 및 잔량으로서 유기용제를 포함하여 이루어진다.In addition, the photoresist composition for exposure to ultraviolet rays according to the present invention is 10 to 20% by weight of the TBS chain extension resin of the general formula (1), 5 to 10% by weight of the photosensitizer, 0.1 to 2% by weight of the additive and the remaining amount as a structural resin It consists of a solvent.

상기 감광제는 디아조나프토퀴논과 같은 퀴논계 화합물이 될 수 있다.The photosensitizer may be a quinone-based compound such as diazonaphthoquinone.

상기 유기용제는 아세톤(Acetone), 메틸에틸케톤(MEK ; Methyl Ethyl Ketone), 시클로헥사논(Cyclohexnone) 및 이소아밀케톤(Isoamyl Ketone) 등의 케톤류, 자일렌(Xylene)과 같은 석유용제류, 엔-부틸아세테이트(n-Butyl Acetate), 에틸셀로솔브 아세테이트(Ethyl Cellosolve Acetate)와 같은 아세테이트류, 에틸락테이트(Ethyl Lactate) 및 이들 중 2이상의 혼합물로 이루어진 그룹 중에서 선택된 것이 될 수 있다.The organic solvents are ketones such as acetone, methyl ethyl ketone (MEK; Methyl Ethyl Ketone), cyclohexanone (Cyclohexnone) and isoamyl ketone, petroleum solvents such as xylene, It may be selected from the group consisting of acetates such as butyl acetate (n-Butyl Acetate) and ethyl cellosolve acetate, ethyl lactate and mixtures of two or more thereof.

또한, 상기 원자외선 노광용 포토레지스트 조성물에는 전사되는 패턴의 콘트라스트와 해상도의 향상을 위하여 트리아졸 또는 테트라졸과 같은 증감제를 더 포함할 수 있다.In addition, the photoresist composition for far ultraviolet exposure may further include a sensitizer such as triazole or tetrazole to improve the contrast and resolution of the pattern to be transferred.

이하, 본 발명을 구체적인 실시예를 참조하여 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to specific examples.

본 발명에 따른 반도체장치의 제조를 위한 공정 중 포토리소그래피공정에서 광원으로서 원자외선을 사용하여 노광할 수 있는 원자외선 노광용 포토레지스트 조성용 구조제 수지는, 하기 화학식1과 같은 티비에스쇄연장수지로 구성된다.In the photolithography step of manufacturing the semiconductor device according to the present invention, the structural resin for the composition of the photoresist for exposure to ultraviolet light that can be exposed using the ultraviolet light as a light source is composed of a TV chain extension resin, such as do.

화학식1Formula 1

상기에서 R1및 R2는 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 5의 알킬기이고, R5는 이소프로필기이며, m은 100 내지 1,000,000의 자연수이고, n은 1 내지 100의 자연수임.In the above, R 1 and R 2 are hydrogen or a methyl group, alkyl group having 1 to 5 carbon atoms such as ethyl group, R 5 is isopropyl group, m is a natural number of 100 to 1,000,000, n is a natural number of 1 to 100.

상기한 티비에스쇄연장수지는 티-부톡시카르보닐옥시스티렌('티비에스'라 한다)을 디술피드를 포함하는 이니퍼(Inifer)를 사용하여 중합시켜 티비에스를 반복단위로 하는 티비에스올리고머를 디티올을 포함하는 커넥터로 쇄연장시켜 수득되는 것으로서, 반복단위가 되는 티비에스를 커넥터로 쇄연장시킨 구조를 갖는다는 뜻으로 티비에스쇄연장수지라 칭하였다.The above-mentioned TBS chain extending resin polymerizes T-butoxycarbonyloxystyrene (referred to as "TV") using an inifer containing disulfide and uses a TBS oligomer as a repeating unit. Is obtained by chain extension with a connector containing a dithiol, and is called a TV chain extension resin in order to have a structure in which a TV which is a repeating unit is chain-extended with a connector.

상기에서 이니퍼라 함은 개시제(Initiator)와 전개제(Transfer)의 합성어로서, 중합에서의 중합의 개시와 전개를 동시에 수행할 수 있는 기능을 갖는 것을 뜻하며, 본 발명에서는 이니퍼로서 디술피드를 포함하는 화합물을 사용하였으며, 또한 커넥터 역시 티비에스를 반복단위로 하는 티비에스올리고머들 사이에 결합되어, 이들 티비에스올리고머들을 포함하는 주쇄를 연장시키는 것으로 사용된다.In the above, the term "initiator" is a compound word of an initiator and a transfer agent, and means that it has a function of simultaneously initiating and developing polymerization in polymerization, and includes disulfide as an inferior in the present invention. In addition, the connector is also used as a connector between the TB oligomers having a TB repeat unit, and is used to extend the main chain including these TB oligomers.

상기한 바와 같은 티비에스쇄연장수지는 산촉매하에서 쉽게 절단될 수 있는 카르보닐기를 포함하는 지방족의 사슬을 주쇄로 하며, 또한 보호기로 티-부톡시기를 포함하고 있으며, 이 티-부톡시기는 광반응 후 모두 탈리되어 수지의 빛이 조사된 영역과 빛이 조사되지 않은 영역 사이에서의 용해도차를 더 증가시킬 수 있다.The TBS chain extension resin as described above is composed of an aliphatic chain containing a carbonyl group which can be easily cleaved under an acid catalyst, and also contains a thi-butoxy group as a protecting group. All of these can be detached to further increase the solubility difference between the light irradiated region and the unirradiated region of the resin.

또한, 수지의 주쇄내에 포함되는 벤젠핵들은 모두 주쇄내에서 비공액 결합을 이루어, 다른 결합들에 영향을 주지 않아 원자외선 영역의 광에 대하여 흡수성을 나타내지 않는다. 더욱이, 보호기로서 티-부톡시기가 포함되어 있기 때문에 종래의 티-부틸옥시카르보닐옥시기(t-BOC ; tert-buthyloxy-carbonyloxy group)를 보호기로 하는 폴리-파라-(티-부틸옥시카르보닐옥시)스티렌(Poly-p-(t-butyloxy-carbonyloxy)styrene)과 광산 발생제(Photoacid Generator)인 오늄염(Onium Salt)의 조합으로 된 포토레지스트나, 티-부틸옥시카르보닐옥시기를 보호기로 하는 폴리비닐히드록시페놀(PVHP ; Poly Vinyl Hydroxy Phenol), 248nm에서 강한 세기를 갖는 광선을 내는 불화크립톤 엑시머 레이저(Krypton Fluoride Eximer Laser)노광용 포토레지스트 및 개량된 노볼락수지에 벤조페논계 감광제(PAC ; Photo Active Cmpounds)를 혼합한 조성물에서 사용된 구조제로서의 수지가 공액구조의 벤젠핵을 포함하며, 그에 의하여 특히 193nm에서 강한 광흡수 현상을 나타내는 문제점을 완전히 해결할 수 있다.In addition, all of the benzene nuclei contained in the main chain of the resin form non-conjugated bonds in the main chain, and do not affect other bonds and thus do not show absorbance to light in the far ultraviolet region. Furthermore, since the thi-butoxy group is included as a protecting group, poly-para- (thi-butyloxycarbonyl having a conventional thi-butyloxycarbonyloxy group (t-BOC; tert-buthyloxy-carbonyloxy group) as a protecting group Photoresist consisting of a combination of poly-p- (t-butyloxy-carbonyloxy) styrene and Onium Salt, a photoacid generator, or a thi-butyloxycarbonyloxy group as a protecting group Polyvinyl hydroxyphenol (PVHP), a photoresist for exposure to light with a strong intensity at 248 nm, and a benzophenone-based photosensitizer (PAC) in an improved novolak resin Resins as structuring agents used in compositions incorporating Photo Active Cmpounds include benzene nuclei of conjugated structure, thereby exhibiting strong light absorption, particularly at 193 nm. Indicating the problem is completely solved.

상기 화학식1과 같은 구조의 티비에스쇄연장수지는 티-부톡시카르보닐옥시스티렌('티비에스'라 한다)을 디술피드를 포함하는 이니퍼(Inifer)를 사용하여 중합시켜 티비에스를 반복단위로 하는 티비에스올리고머를 디티올을 포함하는 커넥터로 쇄연장시켜 수득되는 것으로서, 산촉매하에서 쉽게 절단될 수 있는 카르보닐기를 포함하는 지방족의 사슬을 주쇄로 하며, 또한 보호기로 티-부톡시기를 포함하고 있으며, 이 티-부톡시기는 광반응 후 모두 탈리되어 수지의 빛이 조사된 영역과 빛이 조사되지 않은 영역 사이에서의 용해도차를 더 증가시킬 수 있다.The TBS chain extension resin having the structure shown in Chemical Formula 1 was polymerized with Ti-butoxycarbonyloxystyrene (referred to as 'TV') using an inifer containing disulfide to repeat the TBS. Obtained by chain extension of a TiS oligomer to a connector containing dithiol, having an aliphatic chain containing a carbonyl group that can be easily cleaved under an acid catalyst, and also containing a thi-butoxy group as a protecting group. This thi-butoxy group may be all detached after the photoreaction to further increase the solubility difference between the region irradiated with the resin and the region not irradiated with the light.

또한, 수지의 주쇄내에 포함되는 벤젠핵들은 모두 주쇄내에서 비공액 결합을 이루어, 다른 결합들에 영향을 주지 않아 원자외선 영역의 광에 대하여 흡수성을 나타내지 않는다.In addition, all of the benzene nuclei contained in the main chain of the resin form non-conjugated bonds in the main chain, and do not affect other bonds and thus do not show absorbance to light in the far ultraviolet region.

상기 화학식1과 같은 티비에스쇄연장수지의 제조방법은 하기 화학식2에 나타난 바와 같이 티-부톡시카르보닐옥시스티렌을 디술피드를 포함하는 이니퍼(Inifer)를 사용하여 중합시켜 티비에스를 반복단위로 하는 티비에스올리고머를 합성하고, 하기 화학식3과 같이 상기 티비에스올리고머를 커넥터로서 4-티올-α,α'-알킬벤질-4-티올페닐에스터로 쇄연장시켜 수득될 수 있다.In the manufacturing method of the TBS chain extension resin as in Chemical Formula 1, as shown in the following Chemical Formula 2, thi-butoxycarbonyloxystyrene is polymerized using an inifer containing disulfide (Inifer) to repeat the TBS. It can be obtained by synthesizing a TVS oligomer, and chain extension of the TVS oligomer with 4-thiol-α, α'-alkylbenzyl-4-thiolphenyl ester as a connector as shown in the following formula (3).

화학식2Formula 2

상기에서 R5는 이소프로필기이며, R6및 R7은 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 3의 알킬기이고, m은 100 내지 1,000,000의 자연수임.In the above, R 5 is an isopropyl group, R 6 and R 7 is hydrogen or an alkyl group having 1 to 3 carbon atoms such as methyl group, ethyl group, m is a natural number of 100 to 1,000,000.

화학식3Formula 3

상기에서 R1및 R2는 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 5의 알킬기이고, R5는 이소프로필기이며, R6및 R7은 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 3의 알킬기이고, m은 100 내지 1,000,000의 자연수이고, n은 1 내지 100의 자연수임.In the above, R 1 and R 2 are hydrogen or methyl group, alkyl group of 1 to 5 carbon atoms such as ethyl group, R 5 is isopropyl group, R 6 and R 7 is hydrogen or methyl group, alkyl group of 1 to 3 carbon atoms such as ethyl group And m is a natural number of 100 to 1,000,000, and n is a natural number of 1 to 100.

또한, 본 발명에 따른 원자외선 노광용 포토레지스트 조성물은, 구조제 수지로서 상기 화학식1의 티비에스쇄연장수지 10 내지 20 중량%, 감광제 5 내지 10 중량%, 첨가제 0.1 내지 2 중량% 및 잔량으로서 유기용제를 포함하여 이루어진다.In addition, the photoresist composition for exposure to ultraviolet rays according to the present invention is 10 to 20% by weight of the TBS chain extension resin of the general formula (1), 5 to 10% by weight of the photosensitizer, 0.1 to 2% by weight of the additive and the remaining amount as a structural resin It consists of a solvent.

상기에서 구조제로 사용된 티비에스쇄연장수지는 주쇄내에 비공액 이중결합(Non-Conjugated Double Bond)을 가지며, 비공액 이중결합은 주쇄내의 결합수를 증대시켜 식각공정시 내식각성이 보다 우수한 구조적 특성을 가질 수 있으며, 또한 보호기로 티-부톡시기를 포함하고 있으며, 이 티-부톡시기는 광반응 후 모두 탈리되어 수지의 빛이 조사된 영역과 빛이 조사되지 않은 영역 사이에서의 용해도차를 더 증가시킬 수 있는 성질을 가지며, 상기한 감광제와의 광화학적 반응메카니즘에 의하여 빛의 조사시 사용된 마스크의 패턴에 따라 감광제와 구조제로서의 상기 수지 사이에 산촉매를 주고받는 광화학반응이 일어나 빛이 조사되는 영역과 빛이 조사되지 않는 영역 사이에서 서로 다른 광화학반응을 하여 이들 영역들 사이에서 뚜렷한 용해도차를 나타내게 된다.The TBS extension resin used as the structuring agent has a non-conjugated double bond in the main chain, and the non-conjugated double bond increases the number of bonds in the main chain so that the corrosion resistance during the etching process is better. And a thi-butoxy group as a protecting group, and all of the thi-butoxy groups are desorbed after the photoreaction to further increase the solubility difference between the areas where the resin is irradiated and the areas where the light is not irradiated. It has a property to increase, and the photochemical reaction between the photoresist and the resin as a structural agent occurs depending on the pattern of the mask used for the irradiation of light by the photochemical reaction mechanism with the photosensitive agent, so that the light is irradiated. Different photochemistry between the area being illuminated and the area not being illuminated A it is to exhibit a marked difference in solubility between these regions.

상기 감광제는 디아조나프토퀴논과 같은 퀴논계 화합물이 될 수 있으며, 이러한 감광제들은 모두 당해 기술분야에서 통상의 지식을 갖는 자에게는 용이하게 이해될 수 있는 것들임은 물론 상용적으로 구입하여 사용할 수 있을 정도로 공지된 것들로 이해될 수 있는 것들이다.The photosensitizer may be a quinone-based compound such as diazonaphthoquinone, and all of these photosensitizers may be easily understood by those skilled in the art and may be purchased and used commercially. It is to be understood as well known.

상기 유기용제는 아세톤(Acetone), 메틸에틸케톤(MEK ; Methyl Ethyl Ketone), 시클로헥사논(Cyclohexnone) 및 이소아밀케톤(Isoamyl Ketone) 등의 케톤류, 자일렌(Xylene)과 같은 석유용제류, 엔-부틸아세테이트(n-Butyl Acetate), 에틸셀로솔브 아세테이트(Ethyl Cellosolve Acetate)와 같은 아세테이트류, 에틸락테이트(Ethyl Lactate) 및 이들 중 2이상의 혼합물로 이루어진 그룹 중에서 선택된 것이 될 수 있으며, 역시 당해 기술분야에서 통상의 지식을 갖는 자에게는 용이하게 이해될 수 있는 것들이다.The organic solvents are ketones such as acetone, methyl ethyl ketone (MEK; Methyl Ethyl Ketone), cyclohexanone (Cyclohexnone) and isoamyl ketone, petroleum solvents such as xylene, It may be selected from the group consisting of acetates such as n-Butyl Acetate, Ethyl Cellosolve Acetate, Ethyl Lactate, and mixtures of two or more thereof. Those skilled in the art can be easily understood.

또한, 상기 원자외선 노광용 포토레지스트 조성물에는 전사되는 패턴의 콘트라스트와 해상도의 향상을 위하여 트리아졸 또는 테트라졸과 같은 증감제를 더 포함할 수 있다. 이들 증감제들은 모두 이들을 포함하는 포토레지스트 조성물의 감광도를 조절하여 해상도 특히 콘트라스트를 향상시키는 역할을 하는 것으로 당해 기술분야에서 통상의 지식을 갖는 자에게는 이해되고 있는 것들이다.In addition, the photoresist composition for far ultraviolet exposure may further include a sensitizer such as triazole or tetrazole to improve the contrast and resolution of the pattern to be transferred. All of these sensitizers are understood by those skilled in the art to adjust the photosensitivity of the photoresist composition including them to improve the resolution, in particular the contrast.

또한, 상기한 것들 이외에도 통상의 표면활성제, 가소제 및 염료들이 상기 포토레지스트 조성물 100 중량%에 대하여 0.1 내지 10 중량%의 범위로 더 포함될 수 있으며, 이들은 수득되는 포토레지스트 조성물의 웨이퍼 상에의 코팅특성 등을 개선하고, 포토레지스트 조성물 자체의 안정성을 높이기 위하여 사용되는 것으로 이해될 수 있는 것들이다.Further, in addition to those mentioned above, conventional surfactants, plasticizers and dyes may be further included in the range of 0.1 to 10% by weight relative to 100% by weight of the photoresist composition, and these are the coating properties on the wafer of the obtained photoresist composition. Etc., and those that can be understood to be used to improve the stability of the photoresist composition itself.

실시예1Example 1

상기 화학식2에 나타난 바와 같이 티-부톡시카르보닐옥시스티렌을 디술피드를 포함하는 이니퍼(Inifer)를 사용하여 중합시켜 티비에스를 반복단위로 하는 티비에스올리고머를 합성하고, 수득된 티비에스올리고머를 커넥터로서 디(4-티올-α,α'-알킬벤질)카르보네이트로 쇄연장시켜 수득된 티비에스쇄연장수지 15 중량%, 감광제로서 디아조나프토퀴논 7 중량%, 첨가제로서 비이온성 계면활성제, 가소제, 염료 및 트리아졸을 각각 등량으로 혼합한 혼합물 1 중량% 및 유기용제로서 에틸락테이트 77 중량%를 균질하게 혼합시켜 원자외선 노광용 포토레지스트 조성물을 수득하였으며, 이 포토레지스트 조성물에 대하여 통상의 리소그래피공정에 따라 웨이퍼의 표면에 프라이머로서 헥사메틸디실라잔(HMDS ; Hexamethyldisilazane)를 도포하고, 그 위에 상기에서 수득된 본 발명에 따른 원자외선 노광용 포토레지스트 조성물을 도포하고, 130℃에서 소프트베이크 한 후, 마스크를 대고 193nm의 파장의 원자외선을 사용하여 노광하고, 다시 하드베이크한 후, 현상하여 현상품위를 검사하였다.As shown in Chemical Formula 2, thi-butoxycarbonyloxystyrene was polymerized using Inifer containing disulfide to synthesize a TV oligomer having a TiBs as a repeating unit, and the TiB oligomer obtained To 15% by weight of the TBS chain extension resin obtained by chain extension with di (4-thiol-α, α'-alkylbenzyl) carbonate as a connector, 7% by weight of diazonaphthoquinone as a photosensitizer, and a nonionic interface as an additive. A homogeneous mixture of 1% by weight of a mixture of an active agent, a plasticizer, a dye, and a triazole in equal amounts and 77% by weight of ethyl lactate as an organic solvent was homogeneously mixed to obtain a photoresist composition for ultraviolet exposure. According to the lithography process of hexamethyldisilazane (HMDS; Hexameth) as a primer on the surface of the wafer yldisilazane), the above-described photoresist composition for ultraviolet light exposure according to the present invention obtained above was applied, softbaked at 130 ° C, and then exposed using ultraviolet light having a wavelength of 193 nm with a mask. After hard baking, it developed and inspected the developing quality.

실시예2Example 2

커넥터로서 4-티올-α,α'-알킬벤질-4-티올페닐에스터를 사용하는 것을 제외하고는 실시예1과 동일하게 수행하였다.The same procedure as in Example 1 was conducted except that 4-thiol-α, α'-alkylbenzyl-4-thiolphenylester was used as the connector.

그 결과, 충분히 상용화되어 패턴형성에 적용될 수 있는 정도의 현상품위를 내는 것이 밝혀져 기존의 상용적인 포토레지스트 조성물을 대체하여 보다 우수한 현상이 가능한 정도로 사용할 수 있음이 밝혀졌다.As a result, it has been found to be sufficiently commercialized to give a degree of development that can be applied to pattern formation, and it can be used as much as possible to replace the existing commercial photoresist composition.

따라서, 본 발명에 의하면 193nm 정도의 원자외선에도 충분한 투과성을 가지며, 내식각성이 우수하고, 현상시 패턴의 콘트라스트가 분명하고 높은 해상도를 나타내는 원자외선용 포토레지스트 조성물을 제공하는 효과가 있다.Therefore, according to the present invention, there is an effect of providing a photoresist composition for far ultraviolet rays, which has sufficient transmittance even in about 193 nm ultraviolet ray, is excellent in etching resistance, is clear in pattern contrast during development, and exhibits high resolution.

이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (7)

하기 화학식1과 같은 티비에스쇄연장수지로 구성됨을 특징으로 하는 반도체장치의 제조를 위한 공정 중 포토리소그래피공정에서 광원으로서 원자외선을 사용하여 노광할 수 있는 원자외선 노광용 포토레지스트 조성용 구조제 수지.Structural resin for a photoresist composition for ultraviolet light exposure that can be exposed using ultraviolet light as a light source in a photolithography process in the process for manufacturing a semiconductor device, characterized in that consisting of a TV chain extension resin as shown in formula (1). 화학식1Formula 1 상기에서 R1및 R2는 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 5의 알킬기이고, R5는 이소프로필기이며, m은 100 내지 1,000,000의 자연수이고, n은 1 내지 100의 자연수임.In the above, R 1 and R 2 are hydrogen or a methyl group, alkyl group having 1 to 5 carbon atoms such as ethyl group, R 5 is isopropyl group, m is a natural number of 100 to 1,000,000, n is a natural number of 1 to 100. 하기 화학식2에 나타난 바와 같이 티-부톡시카르보닐옥시스티렌을 디술피드를 포함하는 이니퍼(Inifer)를 사용하여 중합시켜 티비에스를 반복단위로 하는 티비에스올리고머를 합성하고, 하기 화학식3과 같이 상기 티비에스올리고머를 커넥터로서 4-티올-α,α'-알킬벤질-4-티올페닐에스터로 쇄연장시켜 수득됨을 특징으로 하는 원자외선 노광용 포토레지스트 조성용 구조제 수지의 제조방법.As shown in Chemical Formula 2, thi-butoxycarbonyloxystyrene was polymerized using Inifer containing disulfide to synthesize a TV oligomer having TiVs as a repeating unit. A method of producing a structural resin for a photoresist composition for ultraviolet exposure, characterized in that the TBS oligomer is obtained by chain extension of 4-thiol-α, α'-alkylbenzyl-4-thiolphenyl ester as a connector. 화학식2Formula 2 상기에서 R5는 이소프로필기이며, R6및 R7은 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 3의 알킬기이고, m은 100 내지 1,000,000의 자연수임.In the above, R 5 is an isopropyl group, R 6 and R 7 is hydrogen or an alkyl group having 1 to 3 carbon atoms such as methyl group, ethyl group, m is a natural number of 100 to 1,000,000. 화학식3Formula 3 상기에서 R1및 R2는 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 5의 알킬기이고, R5는 이소프로필기이며, R6및 R7은 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 3의 알킬기이고, m은 100 내지 1,000,000의 자연수이고, n은 1 내지 100의 자연수임.In the above, R 1 and R 2 are hydrogen or methyl group, alkyl group of 1 to 5 carbon atoms such as ethyl group, R 5 is isopropyl group, R 6 and R 7 is hydrogen or methyl group, alkyl group of 1 to 3 carbon atoms such as ethyl group And m is a natural number of 100 to 1,000,000, and n is a natural number of 1 to 100. 구조제 수지로서 하기 화학식1의 티비에스쇄연장수지 10 내지 20 중량%, 감광제 5 내지 10 중량%, 첨가제 0.1 내지 2 중량% 및 잔량으로서 유기용제를 포함하여 이루어짐을 특징으로 하는 원자외선 노광용 포토레지스트 조성물.10 to 20% by weight of the TBS chain extension resin of the formula (1), 5 to 10% by weight of the photosensitive agent, 0.1 to 2% by weight of the additive and the remaining amount of the structuring agent resin, characterized in that it comprises an organic solvent Composition. 화학식1Formula 1 상기에서 R1및 R2는 수소 또는 메틸기, 에틸기와 같은 탄소수 1 내지 5의 알킬기이고, R5는 이소프로필기이며, m은 100 내지 1,000,000의 자연수이고, n은 1 내지 100의 자연수임.In the above, R 1 and R 2 are hydrogen or a methyl group, alkyl group having 1 to 5 carbon atoms such as ethyl group, R 5 is isopropyl group, m is a natural number of 100 to 1,000,000, n is a natural number of 1 to 100. 제 3 항에 있어서,The method of claim 3, wherein 상기 감광제가 디아조나프토퀴논과 같은 퀴논계 화합물임을 특징으로 하는 상기 원자외선 노광용 포토레지스트 조성물.The photoresist composition for ultraviolet exposure, characterized in that the photosensitive agent is a quinone-based compound such as diazonaphthoquinone. 제 3 항에 있어서,The method of claim 3, wherein 상기 유기용제가 아세톤(Acetone), 메틸에틸케톤(MEK ; Methyl Ethyl Ketone), 시클로헥사논(Cyclohexnone) 및 이소아밀케톤(Isoamyl Ketone) 등의 케톤류, 자일렌(Xylene)과 같은 석유용제류, 엔-부틸아세테이트(n-Butyl Acetate), 에틸셀로솔브 아세테이트(Ethyl Cellosolve Acetate)와 같은 아세테이트류, 에틸락테이트(Ethyl Lactate) 및 이들 중 2이상의 혼합물로 이루어진 그룹 중에서 선택된 것임을 특징으로 하는 상기 원자외선 노광용 포토레지스트 조성물.The organic solvent is acetone, methyl ethyl ketone (MEK; Methyl Ethyl Ketone), cyclohexanone (Cyclohexnone) and isoamyl ketone, such as ketones, petroleum solvents such as xylene, The above-mentioned far ultraviolet rays, characterized in that selected from the group consisting of acetates such as n-Butyl Acetate, Ethyl Cellosolve Acetate, Ethyl Lactate, and mixtures of two or more thereof. Exposure photoresist composition. 제 3 항에 있어서,The method of claim 3, wherein 상기 원자외선 노광용 포토레지스트 조성물에 트리아졸 또는 테트라졸과 같은 증감제를 더 포함됨을 특징으로 하는 상기 원자외선 노광용 포토레지스트 조성물.The photoresist composition for ultraviolet exposure further comprises a sensitizer such as triazole or tetrazole in the photoresist composition for ultraviolet exposure. 제 6 항에 있어서,The method of claim 6, 상기 증감제가 상기 포토레지스트 조성물 100 중량%에 대하여 0.1 내지 10 중량%가 더 포함됨을 특징으로 하는 상기 원자외선 노광용 포토레지스트 조성물.The photoresist composition for ultraviolet exposure, characterized in that the sensitizer further comprises 0.1 to 10% by weight relative to 100% by weight of the photoresist composition.
KR1019990042848A 1997-05-08 1999-10-05 Base resin for photoresist using ultra-violet ray for fabrication of semiconductor device, its manufacturing method and photoresist using ultra-violet ray comprosing the base resin KR100252225B1 (en)

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